Polymeric 4-vinylcyclohexene dioxide compositions



Patented May 17, 1949 POLYMERIC 4-VINYLCYCLOHEX'ENE DIOXIDE COMPOSITIONSWalter John Hornibrook, McMasterville, Quebec,

Canada, assignor to Canadian Industries Limited, Montreal, Quebec,Canada, a corporation of Canada No Drawing. ApplicationFebruary 20,1948, Se-

rial No. 9,970. In Canada May 30, 1947 13 Claims.

This invention relates to new polymeric 4- vinylcyclohexene dioxidecompositions and to their preparation.

-vinylcyclohexene dioxide is prepared, according to copending U. S.application Serial No. 743,198, filed April 22, 194'? in the names of O.C. W. Allenby and G. J. Harris, by reacting 4-vinylcyclohexene withhypochlorous acid to form 4- vinylcyclohexene dichlorhydrins and by,dehydrohalogenating the dichlorhydrins to obtain the dioxide. Incopending U. S. applications Serial No. 766,453, filed August 5, 1947 inthe name of O. C. W. Allenby and Serial No. 766,455, filed August 5,1947 now Patent No. 2,460,195 in the name of G. H. Segall, there aredisclosed homopolymers of 4-vinylcyclohexene dioxide together withprocesses for preparing those polymers which comprise heating4-vinylcyclohexene dioxide with various polymerization catalysts.

These polymers of 4-vinylcyclohexene dioxide are adapted for a widevariety of uses. However, for certain purposes, the unmodified polymersare not entirely suited despite their possession of some highlyadvantageous properties. This is particularly true in the use of thesepolymers as coatings and films where there is considerable room forimprovement in the flexibility of the polymers.

An object of the present invention is to provide a new polymeric4-vinylcyclohexene dioxide composition and a process of preparing same.A further object is to provide new polymeric compositions having greaterflexibility than unmodified polymeric 4-vinylcyclohexene dioxide. Afurther and more specific object is to provide a polymeric4-vinylcyclohexene dioxide composition particularly adapted for use infilms and castings. Other objects will be apparent from the descriptionof the invention given hereinafter.

The above objects are accomplished according to the present invention bymixing 4-vinylcyclohexene dioxide with a cellulose ester and thenpolymerizing the 4 vinylcyclohexene dioxide. Preferably, the proportionof cellulose ester should be at hast 5%, by weightof the4-vinylcyclohexene dioxide. and should not exceed that amount which willform a compatible mixture with the 4-vinylcyclohexene dioxide. Toincrease the proportion of cellulose ester that will remain incompatible admixture, a volatile organic solvent may be used.

The invention may be carried out by dissolving a cellulose ester in4-vinylcyclohexene dioxide, withor without the aid of a volatile organicsolvent such as acetone. A plasticizer for the cellulose ester, up to100% by weight of the cellulose ester, may optionally be added. Apolymerization catalyst is then added to the solution which ismaintained at a temperature of 20 C. to 110 C. until polymerization issubstantially complete. If a catalyst is unstable, it may be necessaryto cool the solution down to a relatively low temperature before addingthe catalyst and then slowly raising the temperature. To illustrate,perchloric acid is a highly preferred polymerization catalyst and yet itis relatively unstable so that the solution is normally cooled to atemperature of 0 C. to 20 C. before the perchloric acid is added andthen the solution is slowly heated, preferably up to a temperature ofabout C. to C. which temperature is maintained until polymerization iscomplete. Where stable polymerization catalysts such as boric acid orzinc chloride are used, the cooling step is not necessary. 1

The following examples, in which all proportions are given by weightunless otherwise specified, illustrate specific embodiments of theinvention.

Example I A 5% solution of cellulose acetate in 4-vinylcyclohexenedioxide was prepared by dissolving Example II To parts of a 5% solutionof cellulose acetate in 4-vinylcyclohexene dioxide, prepared as inExample I, there was added 2.4 parts of dioctylphthalate as plasticizer,i. e., an amount of plasticizer equal to about 50% of the weight of thecellulose acetate present in the reaction mixture. The solution wascooled to 0 C. and 0.15 part of perchloric acid as a 9% solution inacetic acid was added. The mixture was then slowly heated to 90 C. Afterone hour heating, a gel was obtained which, with continued heating,polymerized within 24 hours to a hard solid.

- Example III A 10% solution of cellulose acetate in -vinyl- Example IVA 5% solution of cellulose nitrate in 4-vinylcyclohexene dioxide wasprepared by dissolving 5 parts of cellulose nitrate in 95 parts of4-vinylcyclohexene dioxide. 100 parts of this solution were then cooledto C. and 0.15 part of perchloric acid as a 9% solution in acetic acidwas added. The reaction mixture was heated slowly up to 90 C. and heldat this temperature. It polymerized within one hour to a clear, hard andalmost colorless solid.

Example V A 10% solution of cellulose nitrate in 4-vinylcyclohexenedioxide was prepared by dissolving 10 parts of cellulose nitrate in 90parts of 4-vinylcyclohexene dioxide. 100 parts of this solution werethen treated as in Example IV. After 2 hours heating at 90 C. a clear,hard, slightly yellow polymer was obtained.

Example VI 100 parts of a 10% solution of cellulose nitrate in4-vinylcyclohexene dioxide prepared as in Example V were mixed with 5parts of dioctyl phthalate as plasticizer, i. e., an amount ofplasticizer equal to about 50% of the weight of the cellulose nitratepresent in the reaction mixture. The solution was then cooled to 0 C.and thereafter treated as in Example IV. After one hour of heating at 90C. a clear, hard and slightly yellow polymer was obtained.

Example VII A 20% solution of cellulose nitrate in 4-vinylcyclohexenedioxide was prepared by dissolving 20 parts of cellulose nitrate in 80parts of 4- vinylcyclohexene dioxide. 100 parts of this solution werethen treated as in Example IV. Within one hour heating at 90 C. therewas obtained an extremely hard, clear and transparent polymer.

Example VIII To 100 parts of a 20% solution of cellulose nitrate in4-vinylcylohexene dioxide, prepared as in Example VII, there were addedv parts of dioctyl phthalate as a plasticizer (about 50% of the weightof the cellulose nitrate present in the reaction mixture). The solutionwas then cooled at 0 C. and further treated as in Example IV. A veryhard polymer was obtained after one hour heating at 90 C. i

It will be understood that the above examples are merely illustrativeand that the invention broadly comprises polymerizing 4-vinylcyclohexenedioxide admixed with a cellulose ester, theproportion of cellulose esterpreferably being such that it is in compatible admixture with the4-vinylcyclohexene dioxide.

The invention comprises mixing the 4-vinylcyclohexene dioxide withcellulose esters broadly. Preferred esters, in addition to celluloseacetate of cellulose ester is the compatibility of the ester with4-vinylcyclohexene dioxide, i. e., the amount of the ester which willdissolve in the 4-vinylcyclohexene dioxide. As shown in Example III, theamount of cellulose ester compatible with the 4- vinylcyclohexenedioxide maybe increased by the use of volatile solvents which may beevaporated oil. prior to disposing the composition in a mold or the liketo be polymerized into a solid body. As cellulose nitrate is soluble in4-vinylcyclohexene dioxide in any proportion that would be practical touse, the employment of an auxiliary solvent for increasing thecompatible proportion of this ester would be unnecessary.

Even where the use of an auxiliary solvent is not necessary to increasethe compatibility of the cellulose ester with the 4-vinylcycloliexenedioxide, it may be advantageous to use a volatile organic solvent suchas acetone for the purpose of reducing'the viscosity of the solution tofacilitate handling it in mechanical operations such as pouring intomolds. Although the compatibility of certain cellulose esters,particularly cellulose nitrate, might permit the use of a higherproportion while still obtaining a. compatible mixture with the4-vinylcyclohexene dioxide, nevertheless the use of a proportion ofcellulose ester substantially greater than 25%, by weight of the4-vinylcyclohexene dioxide, is normally not practical.

Although the foregoing examples were all restricted to the use ofperchloric acid as polymerization catalyst, other polymerizationcatalysts are'suitable for the operation of this invention.

Suitable examples of such compounds are the catalysts used for thepolymerization of 4-vinylcyclohexene dioxide, as described in theaforementioned U. S. applications Serial Nos. 766,453

and 766,455. Those comprise periodic acid, chloric acid, iodic acid,boric acid, ferric chloride, aluminum chloride, zinc chloride, stannicchloride, boron trichloride, silicon tetrachloride, phosphoroustrichloride, arsenic trichloride, antimony trichloride, borontrifiuoride, arsenious oxide, antimony trioxide, phosphorus trioxide,trimethylamine, sodium methoxide, trimethyl borate, dihydroxyfluoroboricacid, sodium perborate and benzoyl peroxide.

The proportion of catalyst will be based on the I 4- vinylcyclohexenedioxide without regard to the cellulose ester present. The preciseproportion of catalyst is not a critical factor in the instant inventionand may vary anywhere from 0.0001% to 10% by weight of the4-vinylcyclohexene dioxide but normally the catalyst will be used in therange of 0.02% to 2%.

Polymerization of the 4-vinylcyclohexene dioxide may be effected at anytemperature from 20 C. to 110 C. although generally a temperature of C.to C. has been found most favorable. At lower temperatures the durationof the polymerization period is, of course, appreciably extended and athigher temperatures some difliculty may be encountered in controllingthe polymerization reaction. Despite this, temperatures as high as C.may be used successfully, particularly where relatively thin films are Iments of this invention diamyl phthalate, tricresyl phosphate, tributylphosphate, butyl stearate, and similar conventional cellulose esterplasticizers. A proportion of plasticizer up to 100% or even more, byweight of the cellulose ester, may be used but it is preferred not toexceed 50% plasticizer as little benefit is obtained by increasing theproportion of plasticizer further.

The polymeric compositions of this invention are adapted for a widevariety of uses. Due to their relative flexibility and lack ofbrittleness, coatings and films of these compositions are particularlyvaluable. However, as cast polymers, these compositions are useful for agreat number of other purposes.

As many apparently widely different embodimay be made without departingfrom the spirit and scope thereof, it is to be understood that theinvention is not limited to the specific embodiments thereof exceptasdefined in the appended claims.

I claim:

1. Process of preparing a polymeric composition which comprises forminga compatible mixture of 4-vinylcyclohexene dioxide and at least 5%, byweight of said 4-vinylcyclohexene dioxide, of a cellulose ester andmaintaining said mixture at a temperature of 20 C.-110 C. in thepresence of a polymerization catalyst until said 4- vinylcyclohexenedioxide is substantially completely polymerized.

2. Process as set forth in claim 1 wherein said mixture is maintained ata temperature of 85 o.-9o 0. until said 4-vinylcyclohexene dioxide issubstantially completely polymerized.

3. Process as set forth in claim 1 wherein said cellulose ester iscellulose nitrate.

4. Process as set'iorth in claim' 1 wherein said cellulose ester iscellulose acetate. 5. Process of preparing a polymeric composition whichcomprises forming a mixture of, by weight, 80 to 95 parts of4-vinylcyclohexene dioxide and 5 to parts of cellulose nitrate andmaintaining said mixture at a temperature of 20 C.-l10 C. in thepresence of a polymerization catalyst until said 4-vinylcyclohexenedioxide is substantially completely polymerized.

6. Process of preparing a polymeric composition which comprises forminga mixture of, by weight, 90 to 95 parts of 4-vinylcyclohexene dioxideand 5 to 10 parts of cellulose acetate and maintaining said mixture at atemperature of 20 C.-110 C. in the presence of a polymerization catalystuntil said 4-vinylcyclohexene dioxide is substantially completelypolymerized.

7. Process of preparing a polymeric composition which comprises forminga compatible mixture of 4-vinylcyclohexene dioxide and at least 5%,

by weight of said 4-vinylcyclohexene dioxide, of

a cellulose ester, cooling said mixture to 0 C. and adding perchloricacid as a polymerization catalyst thereto, heating said mixture to 85C.-90 C., and maintaining said mixture at 85 C.-90 C. until said4-vinylcyclohexene dioxide is substantially completely polymerized.

8. A polymeric composition comprising 4-vinylcyclohexene dioxidepolymerized in compatible admixture with at least 5%, by weight of said4-vinylcyclohexene dioxide, of a cellulose ester.

9. A polymeric composition as recited in claim 8 wherein said celluloseester is cellulose nitrate.

10. A polymeric composition as recited in claim 8 wherein said celluloseester is cellulose acetate.

11. A composition adapted to be polymerized and comprising monomeric4-vinylcyclohexene dioxide in compatible admixture with at least 5%, byweight of said 4-vinylc'yclohexene dioxide, of a cellulose ester.

12. A composition as recited in claim 11 wherein said cellulose ester iscellulose nitrate.

13. A composition as recited in claim 11 wherein said cellulose ester iscellulose acetate.

' WALTER JOHN HORNIBROOK.

No references cited.

